Inorganic fibrous materials are well known and widely used for many purposes (e.g. as thermal or acoustic insulation in bulk, mat, or blanket form, as vacuum formed shapes, as vacuum formed boards and papers, and as ropes, yarns or textiles; as a reinforcing fibre for building materials; as a constituent of brake blocks for vehicles). In most of these applications the properties for which inorganic fibrous materials are used require resistance to heat, and often resistance to aggressive chemical environments.
Inorganic fibrous materials can be either glassy or crystalline. Asbestos is an inorganic fibrous material one form of which has been strongly implicated in respiratory disease.
It is still not clear what the causative mechanism is that relates some asbestos with disease but some researchers believe that the mechanism is mechanical and size related. Asbestos of a critical size can pierce cells in the body and so, through long and repeated cell injury, have a bad effect on health. Whether this mechanism is true or not regulatory agencies have indicated a desire to categorise any inorganic fibre product that has a respiratory fraction as hazardous, regardless of whether there is any evidence to support such categorisation. Unfortunately for many of the applications for which inorganic fibres are used, there are no realistic substitutes.
Accordingly there is a demand for inorganic fibres that will pose as little risk as possible (if any) and for which there are objective grounds to believe them safe.
A line of study has proposed that if inorganic fibres were made that were sufficiently soluble in physiological fluids that their residence time in the human body was short; then damage would not occur or at least be minimised. As the risk of asbestos linked disease appears to depend very much on the length of exposure this idea appears reasonable. Asbestos is extremely insoluble.
As intercellular fluid is saline in nature the importance of fibre solubility in saline solution has long been recognised. If fibres are soluble in physiological saline solution then, provided the dissolved components are not toxic, the fibres should be safer than fibres which are not so soluble. The shorter the time a fibre is resident in the body the less damage it can do. H. Forster in `The behaviour of mineral fibres in physiological solutions` (Proceedings of 1982 WHO IARC Conference, Copenhagen, Volume 2, pages 27-55 (1988)) discussed the behaviour of commercially produced mineral fibres in physiological saline solutions. Fibres of widely varying solubility were discussed.
International Patent Application No. WO87/05007 disclosed that fibres comprising magnesia, silica, calcia and less than 10 wt % alumina are soluble in saline solution. The solubilities of the fibres disclosed were in terms of parts per million of silicon (extracted from the silica containing material of the fibre) present in a saline solution after 5 hours of exposure. The highest value revealed in the examples had a silicon level of 67 ppm. In contrast, and adjusted to the same regime of measurement, the highest level disclosed in the Forster paper was equivalent to approximately 1 ppm. Conversely if the highest value revealed in the International Patent Application was converted to the same measurement regime as the Forster paper it would have an extraction rate of 901,500 mg Si/kg fibre--i.e. some 69 times higher than any of the fibres Forster tested, and the fibres that had the highest extraction rate in the Forster test were glass fibres which had high alkali contents and so would have a low melting point. This is convincingly better performance even taking into account factors such as differences in test solutions and duration of experiment.
International Patent Application No. WO89/12032 disclosed additional fibres soluble in saline solution and discusses some of the constituents that may be present in such fibres. Among such constituents are ZrO.sub.2 and this document claims (among other things) processes using fibres of composition (in weight %):--ZrO.sub.2 0.06-10%; SiO.sub.2 35-70%; MgO 0-50%; CaO 0-64.5%. However the patent actually discloses a much more limited range of zirconia containing materials and these are listed in Table 1 below ranked on silica content. None of the disclosed zirconia containing compositions were tested for shrinkage and hence usefulness in high temperature applications; all that these fibres were tested for was ability to withstand a fire test and Table 1 indicates that the results of this test were not very predictable; there does appear to be a trend with silica content but no trend is discernible with zirconia content.
European Patent Application No. 0399320 disclosed glass fibres having a high physiological solubility.
Further patent specifications disclosing selection of fibres for their saline solubility are European 0412878 and 0459897, French 2662687 and 2662688, PCT WO86/04807 and WO90/02713.
TABLE 1 __________________________________________________________________________ SiO.sub.2 CaO MgO Al.sub.2 O.sub.3 ZrO.sub.2 Fire test SiO.sub.2 CaO MgO Al.sub.2 O.sub.3 ZrO.sub.2 Test wt % wt % wt % wt % wt % Pass/Fail mol % mol % mol % mol % mol % __________________________________________________________________________ 174 63.5 35.55 0.33 0.88 0.21 P 61.83 37.08 0.48 0.5 0.1 178 60 38.3 0.48 0.36 0.54 -- 58.7 40.14 0.7 0.21 0.26 177 59.7 38.7 0.46 0.34 0.50 -- 58.36 40.53 0.67 0.20 0.24 176 59.5 39.1 0.42 0.31 0.42 -- 58.1 40.91 0.61 0.18 0.2 182a 59.4 34.9 2.06 0.38 2.31 P 58.69 36.94 3.03 0.22 1.11 181 59.2 36.6 1.13 0.32 0.83 P 58.8 38.94 1.67 0.19 0.4 179 59.2 37 0.98 0.35 0.58 P 58.74 39.33 1.45 0.2 0.28 175 59.2 39.1 0.41 0.33 0.4 P 57.99 41.03 0.6 0.19 0.19 183 59.05 34.84 3.08 0.3 2.65 P 57.65 36.44 4.48 0.17 1.26 186 59.05 36.94 2.57 0.38 3.27 P 56.63 37.95 3.67 0.21 1.53 191 58.6 33.5 2.72 0.58 3.67 P 58.21 35.65 4.03 0.34 1.78 192 58.4 33.2 2.59 0.65 3.69 P 58.39 35.56 3.86 0.38 1.8 189 58.19 35.39 3.26 0.39 3.36 -- 56.59 36.87 4.73 0.22 1.59 184 57.96 35.17 3.55 0.42 3.11 F 56.44 36.69 5.15 0.24 1.48 190 57.86 35.66 3.22 0.36 3.37 F 56.33 37.19 4.67 0.21 1.6 185 57.8 34.4 3.74 0.56 3.12 F 56.62 36.1 5.46 0.32 1.49 188 57.7 36 3 0.2 3.3 P 56.31 37.64 4.36 0.12 1.57 187 56.88 36.45 4 0.32 3.3 -- 54.86 37.66 5.75 0.18 1.55 193 56.65 31.9 3.35 3.35 4.5 F 56.66 34.18 4.99 1.97 2.19 180 54.3 32.75 10.2 1.29 0.58 F 51.41 33.22 14.39 0.72 0.27 182 46.85 29.2 20.6 2.03 0.84 F 42.42 28.33 27.8 1.08 0.37 __________________________________________________________________________
The refractoriness of the fibres disclosed in these various prior art documents varies considerably. The maximum service temperature of any of the above mentioned fibres (when used as refractory insulation) is up to 815.degree. C. (1500.degree. F.).
Among saline soluble commercial fibres usable at temperatures higher than 815.degree. C. are SUPERWOOL.TM. a fibre manufactured by The Morgan Crucible Company plc and which has a maximum use temperature of 1050.degree. C. and a composition of SiO.sub.2 65 wt %; CaO 29 wt %; MgO 5 wt %; Al.sub.2 O.sub.3 1 wt %. A similar fibre is INSULFRAX.TM. a fibre made by Carborundum Company which has a continuous use limit of 1000.degree. C. (1832.degree. F.) and which melts at 1260.degree. C. (2300.degree. F.). This has a composition of SiO.sub.2 65 wt %; CaO 31.1 wt %; MgO 3.2 wt %; Al.sub.2 O.sub.3 0.3 wt % and Fe.sub.2 O.sub.3 0.3 wt %.
Use of ZrO.sub.2 as a constituent in aluminosilicate fibres to provide high temperature resistance is known (see European 0144349). However it is by no means apparent that this effect is transferable to saline soluble fibres and the disclosure of International Patent Application No. WO89/12032 discussed above would tend to suggest that it is not.
The applicant's earlier International Patent Application WO93/15028 (from which this application claims priority) disclosed saline soluble fibres usable at temperatures in excess of 1000.degree. C. but gave no indication that fibres could be used at still higher temperatures. The applicants have found that some of the fibres disclosed in WO93/15028 (e.g. fibre A2-13 from Table 9 of WO93/15028) are in fact usable at temperatures of up to 1260.degree. C. and even higher. In general the applicants have found that fibres of specified compositions (including zirconia containing fibres) are usable at temperatures up to and beyond 1260.degree. C. The applicants have realised that failure of fibres at high temperature occurs primarily upon devitrification of the fibre; if on devitrification insufficient silica is left the fibres will fail through having a shrinkage of greater than 3.5%. Accordingly the applicants have looked to what materials are formed on devitrification.
In the following where reference is made to a saline soluble fibre this is to be taken as meaning a fibre having a total solubility of greater than 10 ppm in saline solution as measured by the method described below, and preferably having much higher solubility.